Geometric Occupancy and Oxidation State Requirements of Cations in Cobalt Oxides for Oxygen Reduction Reaction

doi:10.1021/acsami.9b00481

IMR OpenIR

	Geometric Occupancy and Oxidation State Requirements of Cations in Cobalt Oxides for Oxygen Reduction Reaction
	Liu, Jing 1; Bao, Hongliang 2; Zhang, Bingsen 3; Hua, Qingfeng 1; Shang, Mingfeng 2; Wang, Jianqiang 2; Jiang, Luhua 1
通讯作者	Wang, Jianqiang(wangjianqiang@sinap.ac.cn) ; Jiang, Luhua(luhuajiang@qust.edu.cn)
	2019-04-03
发表期刊	ACS APPLIED MATERIALS & INTERFACES
ISSN	1944-8244
卷号	11 期号:13 页码:12525-12534
摘要	Cobalt oxides, including spinel Co3O4 and rock-salt CoO, have been widely reported as promising catalysts for oxygen reduction reaction (ORR). However, three types of cobalt ions, i.e., Co2+ in the tetrahedral site (Co-Td(2+)), Co3+ in the octahedral site (Co-Oh(3+)), and Co2+ in the octahedral site (Co-Oh(2+)), are included in these oxides, and the roles of cobalt geometric occupancy and valance states have remained elusive. Here, for the first time, we investigated the effects of cobalt geometric occupancy on the ORR activity by substituting Co-Td(2+) and Co-Oh(3+) of Co3O4 with inactive Zn2+ and Al3+, respectively. The ORR activity decreases in the order of Co3O4 (Co-Oh(3+), Co-Td(2+)) < ZnCo2O4 (Co-Oh(3+)) << CoAl2O4 (Co-Td(2+)) in accordance with the ORR overpotentials at the current density of 0.1 mA cm(Ox)(-2). Furthermore, by comparatively investigating the activity and stability of Co3O4 (Co-Oh(3+)) and CoO (Co-Oh(2+)) nanoparticles, by virtue of the electrochemical technique, the high-resolution transmission electron microscopy, and the in operando fuel cell-X-ray absorption spectroscopy techniques, it was revealed that Co-Oh(2+), in CoO is the main active site, which under electrochemical conditions tends to transform into Co-Oh(3+), and form Co3O4 with a hollow structure due to the Kirkendall effect; nevertheless, it retains decent ORR activity due to the formation of the unique hollow structure.
关键词	cobalt oxide oxygen reduction reaction geometric occupancy valance state octahedral coordination
资助者	Key Research and Development Project of Shandong Province ; National Science Foundation of China ; Taishan Scholars special project funding of Shandong Province
DOI	10.1021/acsami.9b00481
收录类别	SCI
语种	英语
资助项目	Key Research and Development Project of Shandong Province[2017GGX20107] ; National Science Foundation of China[21776146] ; National Science Foundation of China[21576258] ; Taishan Scholars special project funding of Shandong Province[ts201712046]
WOS研究方向	Science & Technology - Other Topics ; Materials Science
WOS类目	Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary
WOS记录号	WOS:000463843900039
出版者	AMER CHEMICAL SOC
引用统计	被引频次：39[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://ir.imr.ac.cn/handle/321006/132784
专题	中国科学院金属研究所
通讯作者	Wang, Jianqiang; Jiang, Luhua
作者单位	1.Qingdao Univ Sci & Technol, Coll Mat Sci & Engn, Nanomat & Electrocatalysis Lab, 53 Zhengzhou Rd, Qingdao 266042, Shandong, Peoples R China 2.Chinese Acad Sci, Shanghai Inst Appl Phys, 239 Zhangheng Rd, Shanghai 201204, Peoples R China 3.Chinese Acad Sci, Inst Met Res, 72 Wenhua Rd, Shenyang 110016, Liaoning, Peoples R China
推荐引用方式 GB/T 7714	Liu, Jing,Bao, Hongliang,Zhang, Bingsen,et al. Geometric Occupancy and Oxidation State Requirements of Cations in Cobalt Oxides for Oxygen Reduction Reaction[J]. ACS APPLIED MATERIALS & INTERFACES,2019,11(13):12525-12534.
APA	Liu, Jing.,Bao, Hongliang.,Zhang, Bingsen.,Hua, Qingfeng.,Shang, Mingfeng.,...&Jiang, Luhua.(2019).Geometric Occupancy and Oxidation State Requirements of Cations in Cobalt Oxides for Oxygen Reduction Reaction.ACS APPLIED MATERIALS & INTERFACES,11(13),12525-12534.
MLA	Liu, Jing,et al."Geometric Occupancy and Oxidation State Requirements of Cations in Cobalt Oxides for Oxygen Reduction Reaction".ACS APPLIED MATERIALS & INTERFACES 11.13(2019):12525-12534.